WO1997046722A1 - Recuperation de fer a partir de flux de materiaux dechets - Google Patents

Recuperation de fer a partir de flux de materiaux dechets Download PDF

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Publication number
WO1997046722A1
WO1997046722A1 PCT/US1997/009852 US9709852W WO9746722A1 WO 1997046722 A1 WO1997046722 A1 WO 1997046722A1 US 9709852 W US9709852 W US 9709852W WO 9746722 A1 WO9746722 A1 WO 9746722A1
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WO
WIPO (PCT)
Prior art keywords
zinc
iron
product solution
solution
oxide
Prior art date
Application number
PCT/US1997/009852
Other languages
English (en)
Inventor
Allan S. Myerson
Charles Burrows
Paul R. Dibella
Original Assignee
Metals Recycling Technologies Corp.
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Filing date
Publication date
Application filed by Metals Recycling Technologies Corp. filed Critical Metals Recycling Technologies Corp.
Priority to JP50087198A priority Critical patent/JP2002508028A/ja
Priority to AU33799/97A priority patent/AU3379997A/en
Priority to EP97929832A priority patent/EP0946767A1/fr
Priority to MXPA98010200A priority patent/MXPA98010200A/es
Publication of WO1997046722A1 publication Critical patent/WO1997046722A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/006—Starting from ores containing non ferrous metallic oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00—Obtaining lead
    • C22B13/04—Obtaining lead by wet processes
    • C22B13/045—Recovery from waste materials
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B17/00—Obtaining cadmium
    • C22B17/04—Obtaining cadmium by wet processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/20—Obtaining zinc otherwise than by distilling
    • C22B19/24—Obtaining zinc otherwise than by distilling with leaching with alkaline solutions, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/20—Obtaining zinc otherwise than by distilling
    • C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/28—Obtaining zinc or zinc oxide from muffle furnace residues
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/34—Obtaining zinc oxide
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
    • C22B3/14—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions containing ammonia or ammonium salts
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/008—Wet processes by an alkaline or ammoniacal leaching
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/02—Working-up flue dust
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
    • Y02P10/134—Reduction of greenhouse gas [GHG] emissions by avoiding CO2, e.g. using hydrogen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S75/00—Specialized metallurgical processes, compositions for use therein, consolidated metal powder compositions, and loose metal particulate mixtures
    • Y10S75/961—Treating flue dust to obtain metal other than by consolidation

Definitions

  • the present invention relates generally to a process for the recovery of usable economically valuable products, including a relatively pure iron or direct reduced iron product and, optionally, an iron oxide and an iron-carbon residual, from industrial waste streams typically comprising zinc compounds and iron compounds.
  • the present invention relates more specifically to a process in which a waste materials stream typically comprising zinc compounds and iron compounds, such as electric arc furnace (EAF) dust, is subjected to a combination of steps including leaching, resulting in a precipitate comprising iron oxides, which then is subjected to roasting, resulting in a direct reduced iron compound which can be used as a feedstock for steel mills.
  • the precipitate containing iron oxides is removed from a process for the recovery of zinc oxide and zinc metal from industrial waste streams.
  • carbon compounds can be added to the waste stream, and a cake product produced from the undissolved iron and carbon compounds, which also can be used as a feedstock for steel mills.
  • the Burrows patent discloses a method to take EAF dust which is mainly a mixture of iron and zinc oxides and, in a series of steps, to separate out and discard the iron oxides and waste metals, so that the resulting zinc-compound-rich solution can be further treated to recover the zinc compounds.
  • Waste metal process dust typically has varying amounts of iron, lead, cadmium and other metals, in various forms, contained in the dust.
  • the first step in the Burrows patent is the treating of the EAF dust with an ammonium chloride solution to leach any zinc oxide, lead oxide and cadmium oxide present in the dust into solution, without any leaching of the iron oxides present.
  • the second step in the Burrows process is cementation in which the solution obtained from the initial leach is filtered to remove any remaining solids and then zinc dust is added.
  • the third step in the Burrows patent then takes the filtrate from the cementation process and cools the filtrate and obtains what are called zinc oxide crystals.
  • the Burrows patent does not teach the treatment or recovery of any values from the discarded iron oxide containing precipitates.
  • U.S. Patent No. 4,071,357 to Peters discloses a method for recovering metal values which includes a steam distillation step and a calcining step to precipitate zinc carbonate and to convert the zinc carbonate to zinc oxide, respectively Peters further discloses the use of a solution containing approximately equal amounts of ammonia and carbon to leach the flue dust at room temperature, resulting in the extraction of only about half of the zinc in the dust, almost 7% of the iron, less than 5% of the lead, and less than half of the cadmium. However, Peters does not disclose a method for further treating the removed components not containing zinc compounds.
  • the present invention satisfies these needs in a method which recovers a relatively pure iron product from waste materials from industrial processes, such as electric arc furnaces, typically containing zinc or zinc oxide.
  • the non-iron solids and feed and product solutions used and/or produced in the process can be recycled such that the process has minimal solid or liquid wastes
  • Other solids can be recovered by treating other compounds in the waste materials, for example zinc oxide, zinc, metal values, and other residues, all of which can be used in other processes
  • the waste matenal typically a fly ash or flue dust such as EAF
  • the waste matenal typically a fly ash or flue dust such as EAF
  • an ammonium chloride solution resulting in a product solution (leachate) and undissolved materials (precipitate)
  • the zinc and/or zinc oxide dissolves in the ammonium chloride solution along with other metal oxides contained in the waste material, such as lead oxide and cadmium oxide
  • the resultant solution is filtered to remove the undissolved materials, including iron oxide
  • the undissolved material separated from the product solution is rich in iron oxides, and typically has some impurities such as zinc fer ⁇ te
  • the undissolved materials can be used without further treatment as a feedstock for steel mills so long as the quantity of impurities is not too great It is preferable, however to remove the impurities from the iron oxide prior to using the iron oxide as a feedstock Even more preferably, reducing the iron oxide to direct reduced iron (DRI) is desired as DRI can be used to replace part or all of the steel scrap charge
  • the iron oxide m the undissolved materials can be reduced to DRI in several manners
  • the undissolved materials may be subjected to a high temperature roasting step, preferably in the 980°C to 1315°C range, to reduce the iron oxide present in the undissolved materials to direct reduced iron Roasting at this elevated temperature oxidizes and/or dirves off the vast majority of the remaining impurities
  • the undissolved materials can be pelietized with carbon or sodium silicate, or another suitable material, at the end of or after the roasting step
  • carbon in the form of activated carbon, carbon dust, carbon pellets or the like, can be introduced to the ammonium chlonde and waste material mixture during the leaching process
  • carbon can be introduced to the dried undissolved material cake When the iron oxide and carbon are heated under a reducing atmosphere, such as CO or CO 2 or other common reducing gases, the carbon will react with the iron oxide, assisting in reducing the iron oxide to DRI Combining any of these methods can result
  • the waste material mixture Prior to being leached by the ammonium chloride solution, the waste material mixture, which typically includes franklinite and magnetite, may be preroasted at temperatures greater than 500°C for a predetermined period of time
  • the preroasting causes a decomposition of the franklinite zinc oxide-iron oxide complex into zinc oxide, iron oxide and other components
  • the preroasting process generally comprises the steps of adding heat to the waste material mixture and/or passing heated reducing gases through the waste material mixture
  • all reducing gases are suitable, hydrogen and carbon-containing gases such as carbon dioxide are preferred, as well as mixing carbon (activated) with the waste material mixture and preroasting in a gas containing oxygen While some iron oxide is reduced from Fe 2 ⁇ and Fe 3 O 4 to FeO, no elemental iron is produced during the preroasting step Additionally, iron and iron oxides are not soluable to any degree in the basic ammonium chloride solution
  • An additional object of the present invention is to provide a method for recovering an iron product from a waste material stream which has been leached with ammonium chloride
  • Still another object of the present invention is to provide a method for recovering iron oxide from waste materials, such as fly ash or flue dust, which contain other metals, such as zinc, lead oxide, and cadmium
  • a further object of the present invention is to provide a method for recovering iron oxide which can be used as is as a feedstock for steel production processes.
  • Another object of the present invention is to provide a method for producing direct reduced iron from iron oxide recovered as a residue from an ammonium chloride leached waste material, such as fly ash or flue dust
  • a final object of the present invention is to provide a method for recovering an iron product such as direct reduced iron and/or iron oxide which is economical, quick and efficient
  • a product By taking an iron cake comprising for the most part iron oxides, and roasting it at elevated temperatures under a reducing atmosphere, a product can be made which is equivalent to direct reduced iron.
  • This direct reduced iron product then can be pelletized with carbon or with a sodium silicate, or other suitable compound, after it comes out of the furnace
  • the final product then can be used as a feedstock for steel mills without any additional treatment.
  • the additional step of roasting the iron cake, which is the undissolved precipitate, to reduce the iron oxide and to drive off any zinc, cadmium, and lead, and other impurities, is added to the end of a zinc oxide recovery process.
  • the resulting iron product may have been reduced from several forms of the iron, such as FeO, Fe 2 ⁇ 3 , or Fe. ⁇ O ⁇ reduced to an iron extremely usable as the feedstock for steel mills
  • the waste material, such as the flue dust, is leached, and the remaining undissolved precipitate is, for the most part, an iron oxide cake.
  • the bond to the non-leachable zinc oxide-iron oxide complex, franklinite, contained in the undissolved precipitate is broken, and the zinc oxide compounds are exhausted in the off gas and captured in a pollution control device, such as a baghouse, leaving the iron oxide cake as the residue
  • a pollution control device such as a baghouse
  • the iron oxide cake is roasted at an elevated temperature, causing the reduction of the iron oxide, leaving the iron metal values.
  • the iron then can be mixed with a binder and formed into briquettes or cubes to be used as the feedstock
  • the exhausted impurities then can be recycled to recover, for example, zinc oxide, cadmium metal, and lead metal
  • the present process is a continuous method for the recovery of iron products from waste material streams
  • the basic process steps comprise Basic Process Steps a treating the waste material with an ammonium chloride solution at an elevated temperature to form a product solution and an undissolved precipitate comprising iron oxide, b separating the product solution from the undissolved precipitate comprising the iron oxide, c further treating the undissolved precipitate in a roasting process resulting in the recovery of a relatively pure iron product
  • additional steps may be added depending on the process conditions and direct reduced iron properties desired
  • the additional steps include, either individually or in some combination
  • elemental carbon can be added during the leaching step or steps to initiate the reduction of the iron oxide into direct reduced iron during the leaching step or steps
  • the elemental carbon may be added in a number of forms including, but not limited to, dust, granules, and pellets
  • the elemental carbon does not go into solution and remains with the undissolved precipitate
  • elemental carbon can be added to the undissolved precipitate after it has been separated from the product solution Combining elemental carbon and iron oxide in this manner at an elevated temperature and under a reducing atmosphere also will initiate the reduction of the iron oxide into direct reduced iron
  • elemental carbon can be mixed into the undissoved precipitate in a number of manners including, but not limited to ribbon blenders and mixers
  • the preroasting step can be carried out prior to the initial leaching step, or between a first and second leaching step, or both
  • the powder containing the franklinite and magnetite, such as the waste dust is heated to temperatures greater than 500°C This temperature causes a reaction which causes a decomposition of the stable franklinite phase into zinc oxide and other components, and yet does not allow for the complete reduction of zinc oxide to zinc metal
  • the resulting zinc oxide can be removed by sublimation or extraction with an ammonium chloride solution, such as bv following the steps detailed above under the general process
  • the resulting material after extraction has less than 1% by weight zinc
  • the dust can be preroasted using many conventional roasting processes, such as, for example, direct or indirect heating and the passing of hot gases through the dust
  • non-explosive mixtures of reducing gases such as hydrogen gas and nitrogen or carbon dioxide
  • hydrogen gas and nitrogen or carbon dioxide can be passed through the powder containing franklinite and magnetite Hydrogen gas is not the only species that may be used for reductive decomposition of franklinite
  • carbon or simple carbon containing species including carbon-containing reducing gases and elemental carbon Heterogeneous gas phase reductions are faster than solid state reductions at lowei temperatures and therefore suggest the use of carbon monoxide
  • the carbon monoxide can be generated in situ by mixing the franklinite powder with carbon and heating in the presence of oxygen at elevated temperatures The oxygen concentration is controlled to optimize CO production
  • the carbon monoxide may be introduced as a separate source to more clearly separate the rate of carbon monoxide preparation from the rate of Franklinite decomposition
  • the prepared zinc oxide then can be removed by either ammonium chloride extraction or sublimation
  • the dust After the dust has been preroasted, it is subjected to a leaching step in 23% by weight ammonium chloride solution in water at a temperature of at least 90°C Any zinc or zinc oxide formed du ⁇ ng the preroasting step dissolves in the ammonium chloride solution The zinc oxide and ammonium chloride solution then is filtered to remove the undissolved material, including the iron oxide
  • ammonium chloride solution in water is prepared in known quantities and concentrations If the two-stage leaching process is used, the feed material, such as the waste material flue dust described in Table I or any other feed material source which contains iron oxide mixed with other metals, is added to the ammonium chloride solution at a temperature of about 90°C or above Otherwise, the feed material first is roasted The majority of the waste material mixture, including any zinc and/or zinc oxide, lead oxide, cadmium oxide, and other metal oxides, dissolves in the ammonium chloride solution The iron oxide does not dissolve in the ammonium chloride solution As an example, the solubility of zinc oxide in ammonium chloride solutions is shown in Table II
  • the zinc oxide, as well as smaller concentrations of lead or cadmium oxide, are removed from the initial dust by the dissolution in the ammonium chloride solution.
  • the solid remaining after this leaching step contains iron oxides and some impurities including zinc, lead, cadmium, and possibly some other impurities
  • the remaining solid then can be roasted in a reducing atmosphere, typically at a temperature greater than 420°C and often at 700°C to 900°C.
  • the reducing atmosphere can be created by using hydrogen gas, simple carbon species gases such as carbon dioxide, or by heating the material in an oxygen containing gas in the presence of elemental carbon
  • the carbon preferably is in the form of dust or pellets. Typical preroasting times are from 30 minutes to 4 hours As discussed above, the waste dust first may be preroasted and second may be leached, omitting the first leaching step
  • the present process also can be operated to produce a high-quality iron-carbon cake as a residual product
  • the iron oxide contained in the waste stream does not go into solution in the ammonium chloride solution, but is filtered from the product solution as undissolved material
  • This iron oxide cake can be used as is as the feedstock to a steel mill, however, as previously discussed, it becomes more valuable if reduced by reaction with elemental carbon to produce an iron-carbon or direct-reduced iron product
  • One preferred method for producing such an iron-carbon or direct- reduced iron product from the waste material comprises the steps of a treating the waste material with an ammonium chloride solution at an elevated temperature to form a product solution which comprises dissolved zinc and dissolved zinc oxide whereby any iron oxide in the waste material will not go into solution, b adding carbon to the product solution whereby the carbon will not go into solution, and then c separating the product solution from the undissolved materials present in the product solution including any of the iron oxide and the carbon
  • a mixture of iron oxide and carbon is used by the steel industry as a feedstock
  • DRI direct-reduced iron
  • DRI can be used to replace part or all of the steel scrap charged to a steel mill
  • DRI is preferred to scrap because it has a known uniform composition and generally contains no residual elements such as chromium, copper, nickel, and tin
  • carbon-enriched iron oxide is melted, it forms a desired foamy slag because it contains both carbon and iron oxide
  • DRI typically runs in the $120 00 per ton range
  • the iron oxide is a residual product of an economical recovery process, such as the recovery of zinc oxide from flue dust described generally below, with the main value of the process being from the zinc oxide product, the iron oxide or direct-reduced iron can be produced more economically Therefore, the iron oxide produced as a residual in this process has significant value
  • the iron oxide and carbon product is pressed into a cake for ease of handling and use.
  • the cake typically contains approximately 82% solids, but may range from 78% to 86% solids and be easily handled and used. Although cakes of less than 78%> solids can be formed, the other 22%+ of material would be product solution which, if the cake is used as a feedstock to a steel mill, would be reintroduced to the steel-making process, which is uneconomical. Likewise, drying the cake to have more than 86%) solids can be uneconomical.
  • the roasting process produces vapors, from the zinc, lead and cadmium and other impurities, that have to be condensed into dust. These impurities can be sent to the baghouse at the end of the steel making process, mixed into the original waste dust, and then sent to the first leaching step, in a recycle fashion Alternatively, the exhaust vapors and dust from the roasting step may be sent to a separate baghouse at a stand alone facility.
  • carbon can be added to the furnace with the iron oxide.
  • the iron oxide cake can be treated in three manners First, carbon can be added to the leaching step and the iron oxide cake will have carbon plus iron oxide The iron oxide-carbon cake can go directly to the steel mill and, if it goes directly to the steel mill, then the reduction of the iron oxide would take place in the steel mill furnace. Second, the iron oxide-carbon cake can be pelletized and roasted to form direct reduced iron The iron oxide precipitate, which typically contains around 80%> solids, is ground up with carbon and formed into pellets, briquettes or cubes and then heated. These pellets, briquettes or cubes then can be introduced to a steel making furnace.
  • the difference in the material that would be introduced to the furnace from the first manner and the second manner is that in the second manner, direct reduced iron is introduced to the steel making furnace, while in the first manner, a combination of iron oxide and carbon is introduced to the steel making furnace.
  • the iron oxide plus carbon can be supplied to the steel mill as is When this carbon enriched iron oxide is melted, it forms a foamy slag, and a foamy slag is desirable in steel making
  • the carbon can be added through a ribbon blender, and then the iron oxide-carbon cake can be introduced either directly into the furnace or, preferably roasted first toform direct reduced iron, which would be preferred for steel making
  • the first manner is the least preferable, that is adding the material itself as a mixture of carbon and iron oxide without any reducing agents mixed in with it.
  • the second most preferable is the third manner, adding the material with carbon added to it either through the leaching step or through a ribbon blender and put directly into the furnace.
  • the most preferable is the second manner, where carbon is added either though the leaching step or a ribbon blender, pelletizing or briquetting it, roasting it, and introducing it to the steel furnace Examples
  • Examples 1 and 2 do not include roasting and Examples 3 and 4 include roasting.
  • the Examples are intended to illustrate the initial treatment of the waste material stream, including the leaching treatment and the initial waste material stream roasting, if employed.
  • Example 2 A metal dust of composition listed in Table I is added to 23% weight NTLC1 solution (30g NH C1 per lOOg H 2 0). 1 gram of dust is used per 10 grams of solution. The solution is heated to a temperature of 90°C and stirred for a period of 1 hour. During this period the zinc oxide in the dust dissolves. The remaining solid, having a composition of approximately 60%> iron oxide, 5%> calcium oxide, 5% manganese, 30%) other materials, is filtered out of the solution. This remaining solid is further treated according to the invention to recover feedstock grade direct reduced iron or iron oxide.
  • Example 3 A dust containing 19.63% Zn, 27.75% Fe, 1.31% Pb, 9.99% Ca, and 0.024% Cd (analysis based on elements not oxides) was leached at 100°C in a 23%o ammonium chloride solution. The solid remaining after the leaching process was dried and analyzed to contain 12.67% Zn, 4.6% Ca, 35.23% Fe, 0.7% Pb, and 0.01% Cd. This material was placed in a quartz boat in the presence of activated carbon and heated at 900°C for two hours in an atmosphere of 95%> N 2 and 5%> O 2 . After two hours, the material was removed and added to a 23% ammonium chloride solution at 100°C.
  • Example 4 The material was filtered and dried at 140°C for one hour to determine its composition. Analysis of this remaining solid was 42.84% Fe, 0.28% Zn, ⁇ 0.1% Pb, and ⁇ 0.01% > Cd. This remaining solid is further treated according to the invention to recover feedstock grade direct reduced iron or iron oxide.
  • Example 4
  • a dust with the composition given in Table I is leached in 23% ammonium chloride solution for 1 hour at 100°C.
  • the solid remaining (which contained 14% Zn) was placed in a quartz boat and heated to 700°C in an atmosphere of 8%> H 2 and 92%) Ar.
  • the material was cooled and reheated at 100°C in 23% ammonium chloride solution at 100°C.
  • the solid was separated, dried and analyzed for zinc. The zinc was found to be less than 1%.
  • the leached-roasted-leached material then can be subjected to the remainder of the general process.
  • Powdered zinc metal alone may be added to the zinc oxide and ammonium chloride solution in order to remove the solid lead and cadmium.
  • the zinc powder typically aggregates to form large clumps in the solution which sink to the bottom of the vessel. Rapid agitation typically will not prevent this aggregation from occurring.
  • any one of a number of water soluble polymers which act as antiflocculants or dispersants may be used
  • a number of surface active materials also will act to keep the zinc powder suspended, as will many compounds used in scale control These materials only need be present in concentrations of 10 - 1000 ppm
  • Suitable materials include water soluble polymer dispersants, scale controllers, and surfactants, such as gnosulfonates, polyphosphates, polyacrylates, polymethacrylates, maleic anhydride copolymers, polymaleic anhydride, phosphate esters and phosponates Flocon 100 and other members of the Flocon series of maleic- based acrylic oiigomers of various molecular weights of watei soluble polymers, produced by FMC Corporation, also are effective Adding the dispersants to a very high ionic strength solution containing a wide variety of ionic species is anathema to standard practice as dis
  • the filtrate may be treated in several manners, two of which are preferred First, the filtrate may be cooled resulting in the crystallization and recovery of zinc oxide Second, the filtrate may be subjected to electrolysis resulting in the generation and recovery of metallic zinc
  • the filtrate then is cooled to a temperature of between about 20°C and 60°C resulting in the crystallization of a mixture of zinc compounds
  • the mixture contains a significant amount of diammo zinc dichloride, or other complex compounds which involves zinc amino complexes, hydrated zinc oxides and hydroxide species Crystallization helps to achieve a high purity zinc oxide of controlled particle size, typically through control of the temperature-time cooling profile Reverse natural cooling, that is cooling the solution slower at the beginning of the cooling period and faster at the end of the cooling period, is preferred to control the nucleation to crystal growth ratio and, ultimately, the crystal size distribution
  • the precipitated crystallized solid is filtered from the solution and washed with water at a temperature of between about 25°C and 100°C
  • the filtered solution is recycled for further charging with feed material
  • the diamino zmc dichloride dissolves in water The solubility of diamino zinc dichloride in water is shown in Table III
  • the zinc oxide may be dried at approximately 100°C 1 o ensure that the material is free of chloride, however, it is preferable to heat the zinc oxide to a higher temperature Diamino zinc dichlo ⁇ de decomposes at 271°C and ammonium chloride sublimes at 340°C Therefore, heating the zinc oxide to a temperature above 271 °C is useful
  • the drying temperature should be kept below approximately 350°C to prevent the sublimation of significant amount of ammonium chloride Therefore, it is preferable to dry the zinc oxide at a temperature in the range of 271 °C to 350°C
  • the zinc oxide should be dried in this temperature range for approximately 2 to 60 minutes, and preferably from 5 to 20 minutes A 10 minute drying time has been found to be a satisfactory average
  • As the zinc, lead and cadmium contained in the feed materials are amphote ⁇ c species, by using ammonium chloride solution these species will go into solution, while any iron oxide present in the feed material will not go into solution
  • Other solutions such as strong basic solutions having a pH
  • the crystallization step of the present process can be done continuously in order to increase the throughput and maximize the zinc oxide yield after the washing and drying step Optional Preroasting Step for Enhanced Zinc Recover)'
  • the zmc dust obtained from various sources have shown by chemical analysis to contain from 20% - 25%> zinc by weight X-ray diffraction indicates clearly the existence of certain crystalline phases in this dust, specifically zinc oxide
  • the positive identification of the iron phase is complicated by the possible structural types (i e spinel type iron phases showing almost identical diffraction patterns)
  • the zinc oxide (as well as smaller concentrations of lead or cadmium oxide) are removed from the initial dust by dissolution in a concentrated ammonium chloride solution (23%> ammonium chloride)

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  • Manufacture And Refinement Of Metals (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

L'invention concerne un procédé pour la récupération de produits à base de fer, en particulier le fer de réduction directe et l'oxyde de fer pouvant être utilisés comme charge dans les aciéries, à partir de flux de déchets industriels contenant du fer. On traite ces flux avec une liqueur d'attaque au chlorure d'ammonium et on dissocie ensuite de cette liqueur les précipités non dissous renfermant les composés ferreux, puis on traite de nouveau lesdits précipités par grillage à température élevée, ce qui permet d'obtenir la ou les charges de fer.
PCT/US1997/009852 1996-06-07 1997-06-04 Recuperation de fer a partir de flux de materiaux dechets WO1997046722A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP50087198A JP2002508028A (ja) 1996-06-07 1997-06-04 廃材の流れからの鉄生成物の回収
AU33799/97A AU3379997A (en) 1996-06-07 1997-06-04 Recovery of iron products from waste material streams
EP97929832A EP0946767A1 (fr) 1996-06-07 1997-06-04 Recuperation de fer a partir de flux de materiaux dechets
MXPA98010200A MXPA98010200A (es) 1996-06-07 1997-06-04 Recuperacion de productos de hierro a partir de corrientes de material de desecho.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/665,043 1996-06-07
US08/665,043 US5683488A (en) 1992-01-15 1996-06-07 Method for producing an iron feedstock from industrial furnace waste streams

Publications (1)

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WO1997046722A1 true WO1997046722A1 (fr) 1997-12-11

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US (1) US5683488A (fr)
EP (1) EP0946767A1 (fr)
JP (1) JP2002508028A (fr)
AU (1) AU3379997A (fr)
CA (1) CA2257910A1 (fr)
MX (1) MXPA98010200A (fr)
WO (1) WO1997046722A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002074778A1 (fr) * 2000-10-27 2002-09-26 Nulex, Inc. Procede de production de chlorure de zinc diammine et utilisation de ce dernier

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5851490A (en) * 1995-05-11 1998-12-22 Metals Recycling Technologies Corp. Method for utilizing PH control in the recovery of metal and chemical values from industrial waste streams
US5846290A (en) * 1996-02-21 1998-12-08 Metals Recycling Technologies Corp. Method for the recovery of group IA salts during the treatment of industrial process waste streams
US6770249B1 (en) 1999-09-27 2004-08-03 Chester W. Whitman Process to selectively recover metals from waste dusts, sludges and ores
WO2006024492A2 (fr) 2004-08-30 2006-03-09 Interstitial Therapeutics Implant medical comprenant des inhibiteurs de la synthese atp
WO2011001282A2 (fr) 2009-06-29 2011-01-06 Bairong Li Procédés de réduction de métaux, procédés métallurgiques et produits et dispositifs
EP2995702A4 (fr) * 2013-05-08 2017-02-22 Kinotech Solar Energy Corporation Procédé de production de zinc
KR101499446B1 (ko) * 2013-07-29 2015-03-09 인하대학교 산학협력단 폐연성인쇄회로기판의 회수 방법
CN115927873A (zh) * 2022-11-24 2023-04-07 东北大学 一种湿法处理次氧化锌烟尘制备氧化锌的方法

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US3262771A (en) * 1963-06-20 1966-07-26 Mcdowell Wellman Eng Co Recovery of steel and zinc from waste materials
US3849121A (en) * 1971-11-30 1974-11-19 W Burrows Zinc oxide recovery process
US4071357A (en) * 1976-09-23 1978-01-31 Hazen Research, Inc. Process for recovering zinc from steel-making flue dust
US5186741A (en) * 1991-04-12 1993-02-16 Zia Patent Company Direct reduction process in a rotary hearth furnace
US5208004A (en) * 1992-01-15 1993-05-04 Metals Recycling Technologies Corp. Method for the recovery of zinc oxide
EP0671477A1 (fr) * 1994-03-07 1995-09-13 SCEGI Sarl Procédé de retraitement de sous-produits de l'industrie métallurgique
WO1996008585A1 (fr) * 1994-09-08 1996-03-21 Metals Recycling Technologies Corporation Procede pour la recuperation de metaux et d'autres composes chimiques utiles
WO1996017090A1 (fr) * 1994-12-02 1996-06-06 Metals Recycling Technologies Corp. Procede de production d'une charge de fer
US5538532A (en) * 1995-03-02 1996-07-23 Complete Recovery Process Methods for recycling electric arc furnace dust

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GB1568362A (en) * 1976-10-05 1980-05-29 Univ Cardiff Heavy metal recovery in ferrous metal production processes
GB1600022A (en) * 1978-05-30 1981-10-14 Univ Cardiff Recovery of heavy metals from flue dusts
CA1152445A (fr) * 1979-06-22 1983-08-23 Derek J. Fray Electrolyse de chlorure de zinc/cadmium
NL8002743A (nl) * 1980-05-13 1981-12-16 Estel Hoogovens Bv Werkwijze voor het verwerken van zink- en loodhoudende gasstof afkomstig van siderurgische processen.
DE3545187C1 (de) * 1985-12-20 1987-07-09 Lentz Harro Verfahren zur Aufarbeitung von Verzinkereistaub einer Feuerverzinkerei
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US5571306A (en) * 1992-01-15 1996-11-05 Metals Recycling Technologies Corp. Method for producing an enriched iron feedstock from industrial furnace waste streams

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Publication number Priority date Publication date Assignee Title
US3262771A (en) * 1963-06-20 1966-07-26 Mcdowell Wellman Eng Co Recovery of steel and zinc from waste materials
US3849121A (en) * 1971-11-30 1974-11-19 W Burrows Zinc oxide recovery process
US4071357A (en) * 1976-09-23 1978-01-31 Hazen Research, Inc. Process for recovering zinc from steel-making flue dust
US5186741A (en) * 1991-04-12 1993-02-16 Zia Patent Company Direct reduction process in a rotary hearth furnace
US5208004A (en) * 1992-01-15 1993-05-04 Metals Recycling Technologies Corp. Method for the recovery of zinc oxide
EP0671477A1 (fr) * 1994-03-07 1995-09-13 SCEGI Sarl Procédé de retraitement de sous-produits de l'industrie métallurgique
WO1996008585A1 (fr) * 1994-09-08 1996-03-21 Metals Recycling Technologies Corporation Procede pour la recuperation de metaux et d'autres composes chimiques utiles
WO1996017090A1 (fr) * 1994-12-02 1996-06-06 Metals Recycling Technologies Corp. Procede de production d'une charge de fer
US5538532A (en) * 1995-03-02 1996-07-23 Complete Recovery Process Methods for recycling electric arc furnace dust

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002074778A1 (fr) * 2000-10-27 2002-09-26 Nulex, Inc. Procede de production de chlorure de zinc diammine et utilisation de ce dernier

Also Published As

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EP0946767A1 (fr) 1999-10-06
JP2002508028A (ja) 2002-03-12
CA2257910A1 (fr) 1997-12-11
US5683488A (en) 1997-11-04
AU3379997A (en) 1998-01-05
MXPA98010200A (es) 2004-02-09

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